US6369093B1 - Pyrazole carboxanilide fungicide - Google Patents

Pyrazole carboxanilide fungicide Download PDF

Info

Publication number
US6369093B1
US6369093B1 US09/786,211 US78621101A US6369093B1 US 6369093 B1 US6369093 B1 US 6369093B1 US 78621101 A US78621101 A US 78621101A US 6369093 B1 US6369093 B1 US 6369093B1
Authority
US
United States
Prior art keywords
carbon atoms
atoms
chlorine
bromine
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US09/786,211
Inventor
Hans-Ludwig Elbe
Astrid Mauler-Machnik
Klaus Stenzel
Karl-Heinz Kuck
Martin Kugler
Thomas Jaetsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Assigned to BAYER AKTIENGESELLSCHAFT PATENTE UND LIZENZEN reassignment BAYER AKTIENGESELLSCHAFT PATENTE UND LIZENZEN ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JAETSCH, THOMAS, KUGLER, MARTIN, KUCK, KARL-HEINZ, STENZEL, KLAUS, MAULER-MACHNIK, ASTRID, ELBE, HANS-LUDWIG
Application granted granted Critical
Publication of US6369093B1 publication Critical patent/US6369093B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/06—Nitrogen directly attached to an aromatic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to novel pyrazole-carboxanilides, to a process for their preparation and to their use for controlling undesirable microorganisms.
  • N-(2-cyclohexyl)-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide, N-(2-phenyl)-1,3-dimethyl-pyrazole-4-carboxanilide and N-[2-(2-fluoro-phenyl)]-1,3-dimethyl-pyrazole-4-carboxanilide can be used for controlling fungi.
  • the activity of these substances is good, however, it is sometimes unsatisfactory at low application rates.
  • n, X and Y are as described may be used for controlling undesirable microorganisms.
  • a) m represents the number 0,
  • n the number 1
  • Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
  • n the number 2 or 3
  • Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
  • X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
  • n integers from 0 to 3 and
  • Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety.
  • Hal represents halogen with aniline derivatives of the formula
  • X, Y, m and n are each as defined above,
  • novel pyrazole-carboxanilides of the formula (I) have very good microbicidal properties and can be used for controlling undesirable microorganisms, both in crop protection and in the protection of materials.
  • the pyrazole-carboxanilides of the formula (I) according to the invention have considerably better fungicidal activity than N-(2-cyclohexyl)-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide, N-(2-phenyl)-1,3-dimethyl-pyrazole-4-carboxanilide and N-[2-(2-fluoro-phenyl)]-1,3-dimethyl-pyrazole-4-carboxanilide, which are the constitutionally most similar active compounds of the prior art of the same direction of action.
  • the formula (I) provides a general definition of the pyrazole-carboxanilides according to the invention.
  • a) m represents the number 0,
  • n the number 1
  • Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
  • n the number 2 or 3
  • Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and
  • X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine, and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4
  • n integers from 0 to 3 and
  • Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and
  • a) m represents the number 0,
  • n the number 1
  • Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
  • n the number 2 or 3
  • Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
  • X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
  • n integers from 0 to 3 and
  • Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl.
  • the formula (II) provides a general definition of the acyl halides required as starting, materials for carrying out the process according to the invention.
  • Hal preferably represents fluorine, chlorine or bromine.
  • acyl halides of the formula (II) are known or can be prepared by known processes (cf. WO 93/11 117 and EP-A 0 776 889).
  • the formula (III) provides a general definition of the aniline derivatives required as reaction components for carrying out the process according to the invention.
  • X, Y, m and n each preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these radicals or these indices.
  • aniline derivatives of the formula (III) are known or can be prepared by known methods (cf. EP-A 0 545 099 and EP-A 0 589 301).
  • Suitable acid binders for carrying out the process according to the invention are all inorganic and organic bases which are customary for such reactions.
  • DABCO diazabicyclo
  • Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrites, such as acetonitrile, pro
  • reaction temperatures can be varied within a relatively wide range.
  • the process is carried out at temperatures between 0° C. and 140° C., preferably between 10° C. and 120° C.
  • the process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate in each case under elevated or reduced pressure.
  • the compounds according to the invention have a potent microbicidal activity and can be employed for controlling undesirable microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • Fungicides are employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides are employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans;
  • Erwinia species such as, for example, Erwinia amylovora;
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae;
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Altemaria species such as, for example, Altemaria brassicae ;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention can be used with particularly good results for controlling diseases in viticulture and in fruit and vegetable growing, such as, for example against Venturia, Botrytis, Sclerobinia, Rhizoctonia, Uncinula, Sphaerotheca, Podosphaera, Altemaria and Colletotriclum species.
  • Rice diseases such as Pyricularia and Pellicularia species are likewise controlled with good results.
  • the active compounds according to the invention are also suitable for increasing the yield of crops. Moreover, they have reduced toxicity and are tolerated well by plants.
  • the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.
  • Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry.
  • industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms.
  • Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.
  • Microorganisms capable of degrading or changing the industrial materials are, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the active compounds or compositions according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium such as Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma such as Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and micro-encapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
  • customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and micro-encapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
  • formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents.
  • extenders that is, liquid solvents, liquefied gases under pressure, and/or solid carriers
  • surfactants that is emulsifiers and/or dispersants, and/or foam formers.
  • the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents.
  • Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulphoxide, or else water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic hydrocarbons such as
  • Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
  • Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates.
  • Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates.
  • Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments for example iron oxide, titanium oxide and Prussian Blue
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be employed in mixtures with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum, or to prevent the development of resistance.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
  • aldimorph ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
  • debacarb debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
  • kasugamycin kasugamycin, kresoxim-methyl
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
  • paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
  • quinconazole quintozene (PCNB)
  • quinoxyfen quinconazole
  • tebuconazole tecloftalam, tecnazene, tetcyclasis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
  • bronopol dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • deltamethrin, demneton M demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,
  • fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
  • Paecilomyces fumosoroseus parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenophos, promecarb, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen,
  • tau-fluvalinate tau-fluvalinate
  • tebufenozide tebufenpyrad
  • tebupirimiphos teflubenzuron
  • tefluthrin temephos, temivinphos, terbufos, tetrachlorvinphos
  • thetacypermethrin thiamethoxam
  • thiapronil thiatriphos
  • thiocyclam hydrogen oxalate thiodicarb
  • thiofanox thuringiensin
  • tralocythrin tralomethrin
  • triarathene triazarnate
  • triazophos triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb
  • vamidothion vaniliprole, Verticillium lecanii
  • Bacillus thuringiensis strain EG-2348 Bacillus thuringiensis strain EG-2348,
  • the active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, spreading, foaming, brushing on and the like. It is further possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation, or the active compound itself, into the soil. The seed of the plants can also be treated.
  • the application rates can be varied within a relatively wide range, depending on the type of application.
  • the application rates of active compound are generally between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha.
  • the application rates of active compound are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the application rates of active compound are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha.
  • compositions used for the protection of industrial materials generally comprise an amount of 1 to 95%, preferably 10 to 75%, of the active compounds.
  • the use concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum rate of application can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the material to be protected.
  • the activity and the activity spectrum of the active compounds to be used according to the invention in the protection of materials, or of the compositions, concentrates or quite generally formulations preparable therefrom, can be increased by, if appropriate, adding other antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for broadening the activity spectrum or obtaining particular effects, such as, for example, the additional protection against insects.
  • These mixtures may have a broader activity spectrum than the compounds according to the invention.
  • Podosphaera test (apple)/protective Solvent 47 parts by weight of acetone
  • Emulsifier 3 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
  • Venturia test (apple)/protective Solvent 47 parts by weight of acetone
  • Emulsifier 3 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at about 21° C. and a relative atmospheric humidity of about 90%.
  • Evaluation is carried out 12 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%.
  • Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

Abstract

Novel pyrazole-carboxanilides of the formula
Figure US06369093-20020409-C00001
in which
X, Y, m and n are each as defined in the description,
a process for preparing these substances and their use for controlling undesirable microorganisms.

Description

This application is a 371 of PCT/EP99/06149 filed Aug. 23, 1999.
FIELD OF THE INVENTION
The present invention relates to novel pyrazole-carboxanilides, to a process for their preparation and to their use for controlling undesirable microorganisms.
BACKGROUND OF THE INVENTION
It is already known that numerous carboxanilides have fungicidal properties (compare WO 93/11 117, EP-A 0 545 099 and EP-A 0 589 301). Thus, N-(2-cyclohexyl)-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide, N-(2-phenyl)-1,3-dimethyl-pyrazole-4-carboxanilide and N-[2-(2-fluoro-phenyl)]-1,3-dimethyl-pyrazole-4-carboxanilide can be used for controlling fungi. The activity of these substances is good, however, it is sometimes unsatisfactory at low application rates.
SUMMARY OF THE INVENTION
Pyrazole-carboxanilides of the formula
Figure US06369093-20020409-C00002
wherein m, n, X and Y are as described may be used for controlling undesirable microorganisms.
DETAILED DESCRIPTION
This invention, accordingly, provides novel pyrazole-carboxanilides of the formula
Figure US06369093-20020409-C00003
in which
a) m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
represents nitro, cyano, hydroxyl, carboxyl, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
 or
b) m represents the number 0,
n represents the number 2 or 3 and
Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
 or
c) m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
n represents integers from 0 to 3 and
Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety.
Furthermore, it has been found that pyrazole-carboxanilides of the formula (I) are obtained by reacting acyl halides of the formula
Figure US06369093-20020409-C00004
in which
Hal represents halogen with aniline derivatives of the formula
Figure US06369093-20020409-C00005
 in which
X, Y, m and n are each as defined above,
if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
Finally, it has been found that the novel pyrazole-carboxanilides of the formula (I) have very good microbicidal properties and can be used for controlling undesirable microorganisms, both in crop protection and in the protection of materials.
Surprisingly, the pyrazole-carboxanilides of the formula (I) according to the invention have considerably better fungicidal activity than N-(2-cyclohexyl)-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide, N-(2-phenyl)-1,3-dimethyl-pyrazole-4-carboxanilide and N-[2-(2-fluoro-phenyl)]-1,3-dimethyl-pyrazole-4-carboxanilide, which are the constitutionally most similar active compounds of the prior art of the same direction of action.
The formula (I) provides a general definition of the pyrazole-carboxanilides according to the invention.
Preference is given to compounds of the formula (I) in which
a) m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
represents nitro, cyano, hydroxyl, carboxyl, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
 or
b) m represents the number 0,
n represents the number 2 or 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
 or
c) m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine, and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
n represents integers from 0 to 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety.
Particular preference is given to compounds of the formula (I) in which
a) m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
represents nitro, cyano, hydroxyl, carboxyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
 or
b) m represents the number 0,
n represents the number 2 or 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
 or
c) m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
n represents integers from 0 to 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl.
The abovementioned definitions can be combined with one another as desired. Moreover, individual definitions may not apply.
Using 1,3-dimethyl-5-fluoropyrazole-4-carbonyl chloride and 2-(4-bromo-phenyl)-aniline as starting materials, the course of the process according to the invention can be illustrated by the formula scheme below.
Figure US06369093-20020409-C00006
The formula (II) provides a general definition of the acyl halides required as starting, materials for carrying out the process according to the invention. In this formula, Hal preferably represents fluorine, chlorine or bromine.
The acyl halides of the formula (II) are known or can be prepared by known processes (cf. WO 93/11 117 and EP-A 0 776 889).
The formula (III) provides a general definition of the aniline derivatives required as reaction components for carrying out the process according to the invention. In this formula, X, Y, m and n each preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these radicals or these indices.
The aniline derivatives of the formula (III) are known or can be prepared by known methods (cf. EP-A 0 545 099 and EP-A 0 589 301).
Suitable acid binders for carrying out the process according to the invention are all inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or else ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). However, it is also possible to carry out the process without an additional acid binder, or to use an excess of the amine component, so that it simultaneously acts as acid binder.
Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitrites, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethyl-formamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane.
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 140° C., preferably between 10° C. and 120° C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate in each case under elevated or reduced pressure.
When carrying out the process according to the invention. in general 1 mol or else an excess of the aniline derivative of the formula (III) and from 1 to 3 mol of acid binder are employed per mole of acyl halide of the formula (II). However, it is also possible to use other ratios of the reaction components. Work-up is carried out by customary methods. In general, the reaction mixture is admixed with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. The residue that remains can, if appropriate, be freed of any impurities that may still be present, using customary methods. such as chromatography or recrystallization.
The compounds according to the invention have a potent microbicidal activity and can be employed for controlling undesirable microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
Fungicides are employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bactericides are employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Some pathogens causing fungal and bacterial diseases which come under the generic names listed above are mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Bremia species, such as, for example, Bremia lactucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Altemaria species, such as, for example, Altemaria brassicae; and
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
The active compounds according to the invention can be used with particularly good results for controlling diseases in viticulture and in fruit and vegetable growing, such as, for example against Venturia, Botrytis, Sclerobinia, Rhizoctonia, Uncinula, Sphaerotheca, Podosphaera, Altemaria and Colletotriclum species. Rice diseases, such as Pyricularia and Pellicularia species are likewise controlled with good results.
The active compounds according to the invention are also suitable for increasing the yield of crops. Moreover, they have reduced toxicity and are tolerated well by plants.
In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.
Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.
Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds or compositions according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.
Microorganisms of the following genera may be mentioned as examples:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, such as Trichoderma viride,
Escherichia. such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa, and
Staphylococcus, such as Staphylococcus aureus.
Depending on their particular physical and/or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and micro-encapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention, as such or in their formulations, can also be employed in mixtures with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum, or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
Examples of co-components in mixtures are the following compounds:
Fungicides:
aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon,
edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-alminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
guazatine,
hexachlorobenzene, hexaconazole, hymexazole,
imazaili, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione,
kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture,
mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,
ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,
paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
quinconazole, quintozene (PCNB), quinoxyfen,
sulphur and sulphur preparations,
tebuconazole, tecloftalam, tecnazene, tetcyclasis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
uniconazole,
validamycin A, vinclozolin, viniconazole,
zarilamide, zineb, ziram and also
Dagger G,
OK-8705,
OK-8801,
α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,
α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,
α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,
(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,
(E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,
isopropyl {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,
1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone-O-(phenylmethyl)-oxime,
1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,
1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,
1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,
1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,
1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,
1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,
1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,
2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,
2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,
2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,
2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,
2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,
2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2-(bromomethyl)-pentanedinitrile,
2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,
2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,
3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,
3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,
3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,
4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,
8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,
8-hydroxyquinoline sulphate,
9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,
bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)oxy]-2,5-thiophenedicarboxylate,
cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,
cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,
ethyl[(4-chlorophenyl)-azo]-cyanoacetate,
potassium hydrogen carbonate,
methanetetrathiol sodium salt,
methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,
methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,
methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,
N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,
N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,
N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,
N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,
N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,
N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,
N-((6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,
N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,
N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,
N-formyl-N-hydroxy-DL-alanine sodium salt,
O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,
O-methyl S-phenyl phenylpropylphosphoramidothioate,
S-methyl 1,2,3-benzothiadiazole-7-carbothioate,
spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran]-3′-one,
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
Insecticides/Acaricides/Nematicides:
abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alphacypermethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben,
cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
deltamethrin, demneton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,
eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimphos,
fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,
granulosis viruses,
halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,
imidacloprid, isazophos, isofenphos, isoxathion, ivermectin,
nuclear polyhedrosis viruses,
lambda-cyhalothrin, lufenuron,
malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, methiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos,
naled, nitenpyram, nithiazine, novaluron,
omethoate, oxamyl, oxydemethon M,
Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenophos, promecarb, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin,
salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,
tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, thetacypermethrin, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazarnate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
vamidothion, vaniliprole, Verticillium lecanii,
YI 5302,
zeta-cypermethrin, zolaprofos,
(1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl 3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,
(3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropane carboxylate,
1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,
2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,
2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,
2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,
2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,
3-methylphenyl propylcarbamate,
4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,
4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,
4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,
4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,
Bacillus thuringiensis strain EG-2348,
[2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,
2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl butanoate,
[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,
dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,
ethyl [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,
N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,
N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,
N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,
N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,
N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,
O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.
It is also possible to admix other known active compounds, such as herbicides or fertilizers and growth regulators.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, spreading, foaming, brushing on and the like. It is further possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation, or the active compound itself, into the soil. The seed of the plants can also be treated.
When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the application rates of active compound are generally between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. In the treatment of seed, the application rates of active compound are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the application rates of active compound are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha.
The compositions used for the protection of industrial materials generally comprise an amount of 1 to 95%, preferably 10 to 75%, of the active compounds.
The use concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimum rate of application can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight, based on the material to be protected.
The activity and the activity spectrum of the active compounds to be used according to the invention in the protection of materials, or of the compositions, concentrates or quite generally formulations preparable therefrom, can be increased by, if appropriate, adding other antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds for broadening the activity spectrum or obtaining particular effects, such as, for example, the additional protection against insects. These mixtures may have a broader activity spectrum than the compounds according to the invention.
The preparation and the use of the substances according to the invention is illustrated by the examples below.
PREPARATION EXAMPLES
Figure US06369093-20020409-C00007
At room temperature, a solution of 2.5 g (0.01 mol) of 2-(4-bromo-phenyl)-aniline in 30 ml of toluene is admixed with 1.0 g (0.01 mol) of triethylamine. At room temperature, 1.8 g (0.01 mol) of 1,3-dimethyl-5-fluoro-pyrazole-4-carbonyl chloride are added with stirring to this mixture. After the addition has ended, the reaction mixture is stirred at room temperature for two hours and then poured into water. The mixture is extracted repeatedly with chloroform. The combined organic phases are dried over sodium sulphate, filtered and concentrated under reduced pressure. The residue that remains is stirred with diisopropyl ether. The resulting crystalline product is filtered off with suction and dried. This gives 1.6 g (41.2% of theory) of N-[2-(4-bromophcnyl)]-1,3-dimethyl-5-fluoro-pyrazole-4-carboxanilide in the form of a solid of melting point 127° C.
The pyrazole-carboxanilides of the formula (I) listed in the table below are likewise prepared in the manner described above.
TABLE 1
(I)
Figure US06369093-20020409-C00008
Ex- ample No.
Figure US06369093-20020409-C00009
 		Physical constant
2
Figure US06369093-20020409-C00010
 		m.p. 100° C.
3
Figure US06369093-20020409-C00011
 		1H-NMR* δ = 2.34 (3H) 3.61 (3H)
4
Figure US06369093-20020409-C00012
 		m.p. 103° C.
5
Figure US06369093-20020409-C00013
 		m.p. 113° C.
6
Figure US06369093-20020409-C00014
 		m.p. 127° C.
7
Figure US06369093-20020409-C00015
 		m.p. 89° C.
8
Figure US06369093-20020409-C00016
 		1H-NMR* δ = 2.38 (3H) 2.45 (3H)
9
Figure US06369093-20020409-C00017
 		m.p. 116° C.
10
Figure US06369093-20020409-C00018
 		m.p. 145° C.
11
Figure US06369093-20020409-C00019
 		m.p. 151° C.
12
Figure US06369093-20020409-C00020
 		m.p. 154° C.
13
Figure US06369093-20020409-C00021
 		m.p. 176° C.
14
Figure US06369093-20020409-C00022
 		m.p. 153° C.
15
Figure US06369093-20020409-C00023
 		m.p. 169° C.
16
Figure US06369093-20020409-C00024
 		m.p. 144° C.
17
Figure US06369093-20020409-C00025
 		m.p. 177° C.
18
Figure US06369093-20020409-C00026
 		m.p. 154° C.
19
Figure US06369093-20020409-C00027
 		oil
20
Figure US06369093-20020409-C00028
 		m.p. 168° C.
21
Figure US06369093-20020409-C00029
 		m.p. 169° C.
22
Figure US06369093-20020409-C00030
 		m.p. 168° C.
23
Figure US06369093-20020409-C00031
24
Figure US06369093-20020409-C00032
 		m.p. 172° C.
*The 1H-NMR spectra were recorded in deuterochloroform (CDCl3) using tetramethylsilane (TMS) as internal standard. What is stated is the chemical shift as δ value in ppm.
USE EXAMPLES Example A
Podosphaera test (apple)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the causative organism of apple mildew Podosphaera leucotricha. The plants are then placed in a greenhouse at about 23° C. and a relative atmospheric humidity of about 70%.
Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
Active compounds, application rates and test results are shown in the table below.
TABLE A
Podosphaera test (apple)/protective
Application rate
of active
compound Efficacy
Active compound in g/ha in %
According to the invention:
(1) 100 100
Figure US06369093-20020409-C00033
(2) 100 96
Figure US06369093-20020409-C00034
(4) 100 97
Figure US06369093-20020409-C00035
(5) 100 99
Figure US06369093-20020409-C00036
(8) 100 98
Figure US06369093-20020409-C00037
(9) 100 100
Figure US06369093-20020409-C00038
Example B
Sphaerotheca test (cucumber)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. Afier the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed at about 23° C. and a relative atmospheric humidity of about 70% in a greenhouse.
Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
Active compounds, application rates and test results are shown in the table below.
TABLE B
Sphaerotheca test (cucumber)/protective
Application rate
of active
compound Efficacy
Active compound in g/ha in %
According to the invention:
(1) 100 95
Figure US06369093-20020409-C00039
(9) 100 94
Figure US06369093-20020409-C00040
Example C
Venturia test (apple)/protective
Solvent: 47 parts by weight of acetone
Emulsifier: 3 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causative organism of apple scab Venturia inaequalis and then remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 1 day.
The plants are then placed in a greenhouse at about 21° C. and a relative atmospheric humidity of about 90%.
Evaluation is carried out 12 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
Active compounds, application rates and test results are shown in the table below.
TABLE C
Venturia test (apple)/protective
Application rate
of active
compound Efficacy
Active compound in g/ha in %
According to the invention:
(1) 100 100
Figure US06369093-20020409-C00041
(8) 100 100
Figure US06369093-20020409-C00042
(9) 100 97
Figure US06369093-20020409-C00043
Example D
Erysiphe test (barley)/protective
Solvent: 48.8 parts by weight of N,N-dimethylformamide
Emulsifier:  1.2 parts by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young cereal plants are sprayed with the preparation of active compound at the stated application rate. 1 day after the treatment, the plants are inoculated with spores of Erysiphe graminis f. sp. hordei. The plants are then placed in a greenhouse at 70% relative atmospheric humidity and a temperature of 18° C.
Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
Active compounds, application rates and test results are shown in the table below.
TABLE D
Erysiphe test (barley)/protective
Application rate
of active
compound Efficacy
Active compound in g/ha in %
(2) 750 90
Figure US06369093-20020409-C00044
(1) 750 100
Figure US06369093-20020409-C00045
(16) 750 94
Figure US06369093-20020409-C00046
(17) 750 100
Figure US06369093-20020409-C00047
Example E
Pyrenophora teres test (barley)/protective
Solvent: 25 parts by weight of N,N-dimethylacetamide
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 48 hours.
The plants are then placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%.
Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
Active compounds, application rates and test results are shown in the table below.
TABLE E
Pyrenophora teres test (barley)/protective
Application rate
of active
compound Efficacy
Active compound in g/ha in %
(1) 250 100
Figure US06369093-20020409-C00048
(8) 250 100
Figure US06369093-20020409-C00049
(9) 250 100
Figure US06369093-20020409-C00050
(17) 250 100
Figure US06369093-20020409-C00051

Claims (14)

What is claimed is:
1. A pyrazole-carboxanilide of the formula
Figure US06369093-20020409-C00052
wherein
a) m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
 or
represents nitro, cyano, hydroxyl, carboxyl, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
 or
b) m represents the number 0,
n represents the number 2 or 3 and
Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
 or
c) m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety,
n represents integers from 0 to 3 and
Y represents halogen, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 5 halogen atoms, alkenyloxy having 2 to 8 carbon atoms, alkinyloxy having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, carbalkoxy having 1 to 8 carbon atoms in the alkoxy moiety or alkoximinoalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety.
2. A pyrazole-carboxanilide of the formula (I) according to claim 1, wherein
a) m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl,
 or
represents nitro, cyano, hydroxyl, carboxyl, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
 or
b) m represents the number 0,
n represents the number 2 or 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
 or
c) m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms or 1 to 5 fluorine, chlorine, and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carbalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety,
n represents integers from 0 to 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine
atoms, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkenyloxy having 2 to 6 carbon atoms, alkinyloxy having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, carboalkoxy having 1 to 4 carbon atoms in the alkoxy moiety or represents alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety.
3. A pyrazole-carboxanilide according to claim 1, having the formula
Figure US06369093-20020409-C00053
4. A pyrazole-carboxanilide according to claim 1, having the formula
Figure US06369093-20020409-C00054
5. A pyrazole-carboxanilide according to claim 1, having the formula
Figure US06369093-20020409-C00055
6. A process for preparing pyrazole-carboxanilides of the formula (I) according to claim 1, comprising the step of reacting acyl halides of the formula
Figure US06369093-20020409-C00056
wherein
Hal represents halogen,
with aniline derivatives of the formula
Figure US06369093-20020409-C00057
 wherein
X, Y, m and n are each as defined in claim 1.
7. A composition for controlling undesirable microorganisms, comprising one or more pyrazole-carboxanilide of the formula (I) according to claim 1, in addition to extenders and/or surfactants.
8. A method for controlling undesirable microorganisms, comprising the step of applying one or more pyrazole-carboxanilides of the formula (I) according to claim 2 to the microorganisms and/or their habitat.
9. A method for controlling undesirable microorganisms, comprising the step of applying one or more pyrazole-carboxanilides of the formula (I) according to claim 1 to the microorganisms and/or their habitat.
10. A process for preparing compositions for controlling undesirable microorganisms, comprising the step of mixing one or more pyrazole-carboxanilides of the formula (I) according to claim 1 with extenders and/or surfactants.
11. A process according to claim 6, wherein the step of reacting acyl halides with aniline derivatives occurs in the presence of an ingredient selected from the group consisting of acid binders, diluents and mixtures thereof.
12. A pyrazole-carboxanilide of the formula (I) according to claim 1, wherein
m represents the number 0,
n represents the number 1 and
Y represents 2-chloro, 2-fluoro, 4-bromo, 2-methyl, 2-trifluoromethyl, 3-trifluoromethyl, or represents nitro, cyano, hydroxyl, carboxyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl.
13. A pyrazole-carboxanilide of the formula (I) according to claim 1, wherein
m represents the number 0,
n represents the number 2 or 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl.
14. A pyrazole-carboxanilide of the formula (I) according to claim 1, wherein
m represents the number 1,
X represents chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl,
n represents integers from 0 to 3 and
Y represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, methylthio, difluoromethoxy, trifluoromethoxy, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl.
US09/786,211 1998-09-04 1999-08-23 Pyrazole carboxanilide fungicide Expired - Lifetime US6369093B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19840322A DE19840322A1 (en) 1998-09-04 1998-09-04 Pyrazole carboxanilides
DE19840322 1998-09-04
PCT/EP1999/006149 WO2000014071A2 (en) 1998-09-04 1999-08-23 Pyrazole carboxanilide fungicide

Publications (1)

Publication Number Publication Date
US6369093B1 true US6369093B1 (en) 2002-04-09

Family

ID=7879781

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/786,211 Expired - Lifetime US6369093B1 (en) 1998-09-04 1999-08-23 Pyrazole carboxanilide fungicide

Country Status (19)

Country Link
US (1) US6369093B1 (en)
EP (1) EP1161420B1 (en)
JP (2) JP2002524449A (en)
KR (1) KR100638003B1 (en)
CN (1) CN1130348C (en)
AR (1) AR020345A1 (en)
AT (1) ATE295353T1 (en)
AU (1) AU5970399A (en)
BR (1) BR9913383B1 (en)
CO (1) CO5210950A1 (en)
DE (2) DE19840322A1 (en)
ES (1) ES2242449T3 (en)
HK (1) HK1045694B (en)
IL (1) IL141210A0 (en)
PL (1) PL200802B1 (en)
PT (1) PT1161420E (en)
RU (1) RU2240314C2 (en)
WO (1) WO2000014071A2 (en)
ZA (1) ZA200101171B (en)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091240A1 (en) * 2002-04-24 2003-11-06 Bayer Cropscience Aktiengesellschaft Methylthiophene carboxanilides
WO2004004460A1 (en) * 2002-07-08 2004-01-15 Basf Aktiengesellschaft Dithianon-based fungicidal mixtures
US20040039043A1 (en) * 2000-07-24 2004-02-26 Hans-Ludwig Elbe Biphenyl carboxamides
US20040053971A1 (en) * 2000-07-24 2004-03-18 Hans-Ludwig Elbe Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesired microorganisms
US20040204470A1 (en) * 2001-07-25 2004-10-14 Hans-Ludwig Elbe Pyrazoylcarboxanilides as fungicides
US20050272785A1 (en) * 2002-04-29 2005-12-08 Ralf Dunkel Biphenyl carboxamides
US20060020243A1 (en) * 2002-09-20 2006-01-26 Ulrich Speck Medical device for dispensing medicaments
US20060142381A1 (en) * 2002-05-23 2006-06-29 Heiko Rieck Furancarboxamides
WO2006120219A1 (en) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Pyrazolocarboxamides as fungicides
US20070109534A1 (en) * 2001-10-29 2007-05-17 Yukihiro Shibata Systems for managing production information
US20070197556A1 (en) * 2004-05-13 2007-08-23 Tormo I Blasco Jordi Fungicidal Mixtures
US20080085924A1 (en) * 2002-12-13 2008-04-10 Bayer Cropscince Ag Biphenylcaboxamides
US7358214B2 (en) 2003-01-29 2008-04-15 Bayer Cropscience Ag Pyrazolyl carboxanilides for controlling unwanted microorganisms
US20080153707A1 (en) * 2005-02-16 2008-06-26 Basf Akitengesellschaft Pyrazolecarboxanilides, Process for Their Preparation and Compositions Comprising Them for Controlling Harmful Fungi
US20080293798A1 (en) * 2005-08-05 2008-11-27 Basf Aktiengelsellschaft Fungicidal Mixtures Comprising Substituted 1-Methylpyrazol-4-Ylcarboxanilides
US20090036509A1 (en) * 2004-06-18 2009-02-05 Basf Aktiengesellschaft N-(Ortho-Phenyl)-1-Methyl -3-Trifluoromethlpyrazole-4-Carboxanilides and Their Use as Fungicides
US20090042724A1 (en) * 2005-06-29 2009-02-12 Jochen Dietz Fungicidal mixtures based on 2,4-disubstituted n-biphenylpyrazolecarboxamides
US20090042725A1 (en) * 2005-07-01 2009-02-12 Basf Aktiengesellschaft Fungicidal Mixtures Based on 3,5-Disubstituted N-Biphenyl-Pyrazolcarboxamides
US20090069398A1 (en) * 2005-12-17 2009-03-12 Bayer Cropscience Ag Pyrazolyl Carboxamides
US20090076113A1 (en) * 2005-12-17 2009-03-19 Bayer Cropscience Ag Biphenylcarboxamides for controlling micro-organisms
US20090203523A1 (en) * 2005-07-06 2009-08-13 Basf Aktiengessellschft Fungicidal Mixtures Made From 1-Methylpyrazol-4-Ylcarboxanilides
US20090233795A1 (en) * 2005-07-05 2009-09-17 Basf Akitengesellschaft Fungicidal Mixtres Based On 3-Monosubstituted N-Bipenyl-Pyrazolecarboxamides
US20090239748A1 (en) * 2005-06-30 2009-09-24 Basf Aktiengesellschaft Fungicidal Mixtures Based on 2,5-Disubstituted N-Biphenylpyrazolcarboxamides
US20090264289A1 (en) * 2006-05-03 2009-10-22 Basf Se Use of Arylcarboxylic Acid Biphenylamides for Seed Treatment
US20100035753A1 (en) * 2007-02-05 2010-02-11 Basf Se Fungicidal Mixtures Comprising Substituted 1-methylpyrazol-4-ylcarboxanilides
US8469943B2 (en) 1995-06-07 2013-06-25 Cook Medical Technologies Llc Coated implantable medical device
US8987470B2 (en) 2010-10-27 2015-03-24 Solvay Sa Process for the preparation of pyrazole-4-carboxamides
US9150461B2 (en) 2010-01-11 2015-10-06 Astarta, Llc Bioorganic agent for treating plants (variants)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY138097A (en) * 2000-03-22 2009-04-30 Du Pont Insecticidal anthranilamides
DE10122447A1 (en) * 2000-07-24 2002-04-18 Bayer Ag biphenylcarboxamides
DE10122097A1 (en) * 2000-07-24 2002-02-07 Bayer Ag Pyrazolylbiphenylcarboxamide
AR036872A1 (en) 2001-08-13 2004-10-13 Du Pont ANTRANILAMIDE COMPOSITE, COMPOSITION THAT INCLUDES IT AND METHOD FOR CONTROLLING AN INVERTEBRATE PEST
TWI312274B (en) 2001-08-13 2009-07-21 Du Pont Method for controlling particular insect pests by applying anthranilamide compounds
KR100866463B1 (en) 2001-08-15 2008-10-31 이 아이 듀폰 디 네모아 앤드 캄파니 Ortho-Substituted Aryl Amides for Controlling Invertebrate Pests
BR0212186A (en) 2001-08-15 2004-10-05 Du Pont Compound, composition and method for invertebrate pest control
ATE417829T1 (en) 2001-08-16 2009-01-15 Du Pont SUBSTITUTED ANTHRANILAMIDES AND THEIR USE AS PESTICIDES
TW200724033A (en) 2001-09-21 2007-07-01 Du Pont Anthranilamide arthropodicide treatment
JP2005505576A (en) 2001-09-21 2005-02-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Anthranilamides for arthropods
JP4317752B2 (en) 2001-10-15 2009-08-19 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Iminobenzoxazine, iminobenzthiazine and iminoquinazoline for controlling invertebrate pests
DE10215292A1 (en) 2002-02-19 2003-08-28 Bayer Cropscience Ag New N-biphenylyl-1-methyl-3-(di- or trifluoromethyl)-1H-pyrazole-4-carboxamides, useful as microbicides, especially fungicides and bactericides for protection of plants or materials such as wood
DE10347090A1 (en) 2003-10-10 2005-05-04 Bayer Cropscience Ag Synergistic fungicidal drug combinations
WO2008053044A2 (en) * 2006-11-03 2008-05-08 Basf Se Hetaryl carbon acid-n-(biphen-2-yl)amide compounds
JP5356754B2 (en) * 2007-09-20 2013-12-04 住友化学株式会社 Aqueous aerosol composition and pest control method using the same
WO2011054733A1 (en) 2009-11-05 2011-05-12 Basf Se Process for preparing aminale and their use for preparing 1,3-disubstituted pyrazole compounds
BR112012010486A2 (en) 2009-11-05 2016-03-15 Basf Se process for preparing compounds 1-3 pyrazole, process for preparing a pyrazolecarboxylic acid of the formula and process for preparing a compound of the formula v
JP2013023476A (en) * 2011-07-22 2013-02-04 Sagami Chemical Research Institute Method for producing 5-fluoro-1h-pyrazole-4-carboxylic acids

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993011117A1 (en) 1991-12-06 1993-06-10 Monsanto Company Pyrazole carboxanilide fungicides
EP0589301A1 (en) 1992-09-21 1994-03-30 BASF Aktiengesellschaft Carboxynilides derivatives, process for their preparation and fungicidal compositions containing them
US5480897A (en) 1991-11-22 1996-01-02 Basf Aktiengesellschaft Anilide derivatives and their use for combating botrytis
WO1997008148A1 (en) 1995-08-30 1997-03-06 Basf Aktiengesellschaft Heterocyclically substituted biphenylamide derivatives, their preparation and their use as fungicides
JPH09132567A (en) 1995-11-08 1997-05-20 Mitsui Toatsu Chem Inc Pyrazolecarboxylic acid anilide derivative and agricultural and horticultural fungicide comprising the same as active ingredient
EP0776889A1 (en) 1995-12-01 1997-06-04 Bayer Ag Process for the production of 1,3-dimethyl-5-fluoro-pyrazol-4-carboxanilides
WO1998003500A1 (en) 1996-07-24 1998-01-29 Bayer Aktiengesellschaft Carbanilides used as pesticides
WO1999009013A1 (en) 1997-08-15 1999-02-25 Basf Aktiengesellschaft Fluoropyrazole-biphenylamide fungicides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6348269A (en) * 1986-08-19 1988-02-29 Sumitomo Chem Co Ltd Pyrazolecarboxamide compound and fungicide comprising said compound as active ingredient

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5480897A (en) 1991-11-22 1996-01-02 Basf Aktiengesellschaft Anilide derivatives and their use for combating botrytis
US5556988A (en) 1991-11-22 1996-09-17 Basf Aktiengesellschaft Anilide derivatives and their use for combating botrytis
US5589493A (en) 1991-11-22 1996-12-31 Basf Aktiengesellschaft Anilide derivatives and their use for combating botrytis
WO1993011117A1 (en) 1991-12-06 1993-06-10 Monsanto Company Pyrazole carboxanilide fungicides
EP0589301A1 (en) 1992-09-21 1994-03-30 BASF Aktiengesellschaft Carboxynilides derivatives, process for their preparation and fungicidal compositions containing them
WO1997008148A1 (en) 1995-08-30 1997-03-06 Basf Aktiengesellschaft Heterocyclically substituted biphenylamide derivatives, their preparation and their use as fungicides
JPH09132567A (en) 1995-11-08 1997-05-20 Mitsui Toatsu Chem Inc Pyrazolecarboxylic acid anilide derivative and agricultural and horticultural fungicide comprising the same as active ingredient
EP0776889A1 (en) 1995-12-01 1997-06-04 Bayer Ag Process for the production of 1,3-dimethyl-5-fluoro-pyrazol-4-carboxanilides
WO1998003500A1 (en) 1996-07-24 1998-01-29 Bayer Aktiengesellschaft Carbanilides used as pesticides
WO1999009013A1 (en) 1997-08-15 1999-02-25 Basf Aktiengesellschaft Fluoropyrazole-biphenylamide fungicides
US6147104A (en) 1997-08-15 2000-11-14 Basf Aktiengesellschaft Fluoropyrazole-biphenylamide fungicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Database Chemabs, Chemical Abstracts Service, Columbus, Ohio, Yoshikawa, Yukihiro et al: "Preparation of pyrazolecarboxyanilide derivatives as agrochemical fungicides" retrieved from STN Database accession No. 127:5086 XP002135650, & JP 09 132567 A (Mistsui Toatsu Chemicals, Inc., Japan, May 20, 1997.

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8469943B2 (en) 1995-06-07 2013-06-25 Cook Medical Technologies Llc Coated implantable medical device
US7176228B2 (en) * 2000-07-24 2007-02-13 Bayer Cropscience Ag Pyrazole biphenylcarboxamides
US20040039043A1 (en) * 2000-07-24 2004-02-26 Hans-Ludwig Elbe Biphenyl carboxamides
US20040053971A1 (en) * 2000-07-24 2004-03-18 Hans-Ludwig Elbe Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesired microorganisms
US7348350B2 (en) 2000-07-24 2008-03-25 Bayer Cropscience Ag Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesirable microorganisms
US6992098B2 (en) 2000-07-24 2006-01-31 Bayer Cropscience Ag Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesired microorganisms
US20040204470A1 (en) * 2001-07-25 2004-10-14 Hans-Ludwig Elbe Pyrazoylcarboxanilides as fungicides
US7538073B2 (en) 2001-07-25 2009-05-26 Bayer Cropscience Ag Pyrazoylcarboxanilides as fungicides
US7299147B2 (en) 2001-10-29 2007-11-20 Hitachi, Ltd. Systems for managing production information
US20070109534A1 (en) * 2001-10-29 2007-05-17 Yukihiro Shibata Systems for managing production information
US7381688B2 (en) 2002-04-24 2008-06-03 Bayer Cropscience Ag Methylthiophene carboxanilides
WO2003091240A1 (en) * 2002-04-24 2003-11-06 Bayer Cropscience Aktiengesellschaft Methylthiophene carboxanilides
US20050272785A1 (en) * 2002-04-29 2005-12-08 Ralf Dunkel Biphenyl carboxamides
US7208169B2 (en) 2002-04-29 2007-04-24 Bayer Cropscience Lp Biphenyl carboxamides
US7179840B2 (en) 2002-05-23 2007-02-20 Bayer Cropscience Ag Furancarboxamides
US20060142381A1 (en) * 2002-05-23 2006-06-29 Heiko Rieck Furancarboxamides
WO2004004460A1 (en) * 2002-07-08 2004-01-15 Basf Aktiengesellschaft Dithianon-based fungicidal mixtures
US20050239848A1 (en) * 2002-07-08 2005-10-27 Eberhard Ammermann Dithianon-based fungicidal mixtures
US7238362B2 (en) 2002-07-08 2007-07-03 Basf Aktiengesellschaft Dithianon-based fungicidal mixtures
US20060020243A1 (en) * 2002-09-20 2006-01-26 Ulrich Speck Medical device for dispensing medicaments
US9649476B2 (en) 2002-09-20 2017-05-16 Bayer Intellectual Property Gmbh Medical device for dispersing medicaments
US8439868B2 (en) 2002-09-20 2013-05-14 Bayer Pharma AG Medical device for dispersing medicaments
US8257305B2 (en) 2002-09-20 2012-09-04 Bayer Pharma Aktiengesellschaft Medical device for dispensing medicaments
US20080085924A1 (en) * 2002-12-13 2008-04-10 Bayer Cropscince Ag Biphenylcaboxamides
US7728019B2 (en) 2002-12-13 2010-06-01 Bayer Cropscience Ag Biphenylcarboxamides
US7358214B2 (en) 2003-01-29 2008-04-15 Bayer Cropscience Ag Pyrazolyl carboxanilides for controlling unwanted microorganisms
US20070197556A1 (en) * 2004-05-13 2007-08-23 Tormo I Blasco Jordi Fungicidal Mixtures
US20090036509A1 (en) * 2004-06-18 2009-02-05 Basf Aktiengesellschaft N-(Ortho-Phenyl)-1-Methyl -3-Trifluoromethlpyrazole-4-Carboxanilides and Their Use as Fungicides
US20080153707A1 (en) * 2005-02-16 2008-06-26 Basf Akitengesellschaft Pyrazolecarboxanilides, Process for Their Preparation and Compositions Comprising Them for Controlling Harmful Fungi
US8008232B2 (en) * 2005-02-16 2011-08-30 Basf Aktiengesellschaft Pyrazolecarboxanilides, process for their preparation and compositions comprising them for controlling harmful fungi
US7799334B2 (en) 2005-05-11 2010-09-21 Basf Aktiengesellschaft Pyrazolecarboxamides
WO2006120219A1 (en) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Pyrazolocarboxamides as fungicides
US20090036305A1 (en) * 2005-05-11 2009-02-05 Basf Aktiengesellschaft Pyrazolecarboxamides
US20090042724A1 (en) * 2005-06-29 2009-02-12 Jochen Dietz Fungicidal mixtures based on 2,4-disubstituted n-biphenylpyrazolecarboxamides
US20090239748A1 (en) * 2005-06-30 2009-09-24 Basf Aktiengesellschaft Fungicidal Mixtures Based on 2,5-Disubstituted N-Biphenylpyrazolcarboxamides
US20090042725A1 (en) * 2005-07-01 2009-02-12 Basf Aktiengesellschaft Fungicidal Mixtures Based on 3,5-Disubstituted N-Biphenyl-Pyrazolcarboxamides
US20090233795A1 (en) * 2005-07-05 2009-09-17 Basf Akitengesellschaft Fungicidal Mixtres Based On 3-Monosubstituted N-Bipenyl-Pyrazolecarboxamides
US20090203523A1 (en) * 2005-07-06 2009-08-13 Basf Aktiengessellschft Fungicidal Mixtures Made From 1-Methylpyrazol-4-Ylcarboxanilides
US8153819B2 (en) 2005-08-05 2012-04-10 Basf Se Fungicidal mixtures comprising substituted 1-methylpyrazol-4-ylcarboxanilides
US20080293798A1 (en) * 2005-08-05 2008-11-27 Basf Aktiengelsellschaft Fungicidal Mixtures Comprising Substituted 1-Methylpyrazol-4-Ylcarboxanilides
US7799739B2 (en) 2005-12-17 2010-09-21 Bayer Cropscience Ag Biphenylcarboxamides for controlling micro-organisms
US20090076113A1 (en) * 2005-12-17 2009-03-19 Bayer Cropscience Ag Biphenylcarboxamides for controlling micro-organisms
US20090069398A1 (en) * 2005-12-17 2009-03-12 Bayer Cropscience Ag Pyrazolyl Carboxamides
US20090264289A1 (en) * 2006-05-03 2009-10-22 Basf Se Use of Arylcarboxylic Acid Biphenylamides for Seed Treatment
US20100035753A1 (en) * 2007-02-05 2010-02-11 Basf Se Fungicidal Mixtures Comprising Substituted 1-methylpyrazol-4-ylcarboxanilides
US9150461B2 (en) 2010-01-11 2015-10-06 Astarta, Llc Bioorganic agent for treating plants (variants)
US8987470B2 (en) 2010-10-27 2015-03-24 Solvay Sa Process for the preparation of pyrazole-4-carboxamides

Also Published As

Publication number Publication date
JP2011144187A (en) 2011-07-28
HK1045694A1 (en) 2002-12-06
KR100638003B1 (en) 2006-10-23
CO5210950A1 (en) 2002-10-30
PT1161420E (en) 2005-08-31
DE59912053D1 (en) 2005-06-16
JP2002524449A (en) 2002-08-06
PL346867A1 (en) 2002-03-11
IL141210A0 (en) 2002-02-10
ZA200101171B (en) 2002-02-12
DE19840322A1 (en) 2000-03-09
PL200802B1 (en) 2009-02-27
EP1161420B1 (en) 2005-05-11
AU5970399A (en) 2000-03-27
CN1130348C (en) 2003-12-10
CN1356985A (en) 2002-07-03
ES2242449T3 (en) 2005-11-01
BR9913383B1 (en) 2011-05-31
RU2240314C2 (en) 2004-11-20
BR9913383A (en) 2001-05-22
AR020345A1 (en) 2002-05-08
KR20010079628A (en) 2001-08-22
WO2000014071A3 (en) 2000-07-13
ATE295353T1 (en) 2005-05-15
WO2000014071A2 (en) 2000-03-16
HK1045694B (en) 2004-09-10
EP1161420A2 (en) 2001-12-12

Similar Documents

Publication Publication Date Title
US6369093B1 (en) Pyrazole carboxanilide fungicide
US7176228B2 (en) Pyrazole biphenylcarboxamides
US7388097B2 (en) Difluoromethyl thiazolyl carboxanilides
US7348350B2 (en) Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesirable microorganisms
US6310005B1 (en) Isothiazole carboxylic acid amides
JP2004534019A (en) Triazolopyrimidines
US7179840B2 (en) Furancarboxamides
US8188129B2 (en) (−)-enantiomer of the 2-[2-(1-chloro-cyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione
US7119049B2 (en) Oxathiinecarboxamides
US6403600B1 (en) Methoximinophenylacetic acid amides
US20050080123A1 (en) Nematicidal trifluorobutenyl imidazole thioether derivatives
JP2003507360A (en) Aminosalicylic acid amides and their use for controlling plant harmful organisms
US20030125325A1 (en) Pyrazolyl benzyl thioethers
US6384066B1 (en) Sulphonyltriazol derivatives and their use for combating micro-organisms
US6359142B1 (en) Sulfonyl oxazolones and their use for combating undesirable microorganisms
US20050033050A1 (en) Phthalazinones and the use thereof in order to combat undesirable microorganisms
US6787670B1 (en) Glyoxyl acid amides, method for producing them and their use for controlling harmful organisms
US6369111B1 (en) Substituted oximes
US20040242662A1 (en) Azinyl sulfonylimidazoles for use as microbicidal agents
US6821927B1 (en) Hydroxamic acid derivatives
WO2002051822A2 (en) Isothiazolecarboxamides as microbicides
US20050049285A1 (en) Dichloropyridyl methyl cyanamidines
ZA200100639B (en) Methoximinophenylacetic acid amides.
WO2003031420A1 (en) Isothiazole derivatives
US20040077880A1 (en) Sulfonylpyrroles

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER AKTIENGESELLSCHAFT PATENTE UND LIZENZEN, GER

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ELBE, HANS-LUDWIG;MAULER-MACHNIK, ASTRID;STENZEL, KLAUS;AND OTHERS;REEL/FRAME:011789/0730;SIGNING DATES FROM 20010123 TO 20010213

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 12